Hearty Congratulation for the 6th Global Chinese Symposium of Chemical Engineering

State Key Lab of Chem. Eng. Dept. of Chem. Eng., Tsinghua Univ.

Studies on Separation

Process Intensification for

Low Carbon Development Weiyang Fei,

State Key Lab of Chem. Eng.,

Dept. of Chem. Eng.,

Tsinghua University, Beijing China

E-mail: fwy-dce@tsinghua.edu.cn

Studies on Separation PI

for Low Carbon Development

• Introduction

• Separation Process Intensification

• Case Studies

• Summary

SUSTAINABLE DEVELOPMENT

• Mrs G·H·Brundtland mentioned in “Our

common Future” in 1987： “Sustainable

development is development that meets the

needs of the present without compromising the

ability of future generations to meet their own

needs.”

• Sustainable development means green

development, circular development and low

carbon development nowadays.

Observed Changes in the Climate System

• Warming of the climate system is unequivocal, and

since the 1950s, many of the observed changes are

unprecedented over decades to millennia. The

atmosphere and ocean have warmed, the amounts of

snow and ice have diminished, sea level has risen,

and concentrations of greenhouse gases have

increased

• Each of the last three decades has been successively

warmer at the Earth’s surface than any preceding

decade since 1850 (see Figure SPM.1). In the

Northern Hemisphere, 1983–2012 was likely the

warmest 30-year period of the last 1400 years

(medium confidence).

CO2 in atmosphere increased very fast since 1750

( Etheridge et al., 1998)

CO2 concentration in atmosphere reached

400ppm in 2013

Global CO2 Reductions

It is one of the gravest challenges for global

sustainable development;

In order to control the Global

Warming less than 2°C, 450 ppmv

CO2 stabilisation corridor would

required in 2050;

global CO2 emission reductions

of around 50 to 60% by 2050

and about 80% by 2100.

The challenge to keep global warming below 2 °C Nature Climate Change 3, 4– 6 (2013) Glen P. Peters & etc., Center for International Climate and Environmental Research – Oslo (CICERO), Oslo, Norway

• The latest carbon dioxide emissions continue to track the high end of emission scenarios, making it even less likely global warming will stay below 2 °C.

• A shift to a 2 °C pathway requires immediate significant and sustained global mitigation, with a probable reliance on net negative emissions in the longer term.

China is a developing country with huge

population. Coal-dominated energy cause huge

CO2 emission;

The CO2 emission per capita in China is still

much lower than those of the developed countries,

however, China became world's leading emitter

since 2006 and its CO2 emission still grew;

Chinese professors and engineers put much

efforts on CCS, but its cost is still very high

( about 60-100$/per T CO2 );

CO2 Capture is most expensive one among the

CCS, therefore, its PI is very important;

雾霾天气的影响

The truth about the

climate crisis is an

inconvenient one

that means we are

going to have to

change the way we

live our lives.

-------Al Gore

An inconvenient truth

Studies on Separation PI

for Low Carbon Development

• Introduction

• Separation Process Intensification

• Case Studies

• Summary

Importance of Chemistry

•On 31 Dec. 2008, UN 63rd general assembly pass through a resolution: the year 2011 is

the year of chemistry.

•Motto: Chemistry- our life, our future http://www.chemistry2011.org

http://www.iyc2011.cn

Chemical Based Industry

• Chemical Industries is essential for human life.

• It is important for Energy, Resource, material, environmental, bio-technology, agriculture and etc.

Energy consumptions is too high in China

0

200

400

600

800

1000

1200

1400

火电(g/kw.h) 钢铁(kgce/t) 乙烯(kgce/t) 合成氨(kgce/t) 水泥(kgce/t)

中国2003 世界水平

Challenges • Globe Warming;

• Energy & Resource shortage;

• Water Crisis;

• Air pollution;

• ……

Separation science and technology, such as distillation,

absorption, extraction, membrane and novel

separation technologies, will pay important roles

for the sustainable development of high value

chemical products and advance process industries.

Chem. Eng. Like a 3D Magic Box Tom Van Gerven† and Andrzej Stankiewicz, Structure, Energy, Synergy, Times The

Fundamentals of Process Intensification, Ind. Eng. Chem. Res. 2009, 48, 2465–2474

Separation Process & CCS

Low CO2 concentrations and pressures leads to very large equipment sizes;

Contaminants such as NOx and SOx and O2 leads to high solvent loss and corrosion;

Energy consumption for solvent regeneration is very high, therefore, the cost of CO2 capture is about 80% of CCS;

The capture of Billion Tons CO2 from Flue Gas is a challenge for separation science & Technology;

A large 5000MW coal power station in east China

Which produces about 30 million ton CO2 per year

Advantage of Pre-combustion CO2 Capture

IGCC with CCS is the best clear coal technology

Costs for existing pre-combustion CO2

capture technologies are still too high. It is

essential to carry on R & D for breakthrough

Process Intensification • The term “Process Intensification” refers

to technologies that replace large,

expensive, energy-intensive equipment

or processes with ones that are smaller,

less costly and more efficient, or that

combine multiple operations into fewer

devices (or a single apparatus).

--------Tsouris (ORNL) and Porcelli (JVP), Chemical Engineering

Progress, 2003, 99(10), pp50

Recent Advances on PI

• CAD 、CFD & etc.;

• Novel Processes;

• Hybrid Processes;

• Multi-Scale study of SP;

• Safety & Sustainable development;

Studies on Separation PI

for Low Carbon Development

• Introduction

• Separation Process Intensification

• Case Studies

• Summary

Case Studies

• Case Study 1: Studies on Process Intensification for

Pre-combustion CO2 Capture

• Case Study 2: Developing NRDC Based on LDV and

CFD

• Case Study 3: Studies of Separation Process

Intensification for value adding

Case Study 1: Studies on Process Intensification

for Pre-combustion CO2 Capture

1. New, Green Absorbents--DMC;

2. High Efficient Separation Equipments---

SMR &PFMR;

3. Hybrid Solvent Regeneration Process

Using Membrane;

4. Process optimization;

Importance of equipment for CO2 Capture

Feasibility studies show that the equipment sizes for

post combustion CO2 capture is huge. Even for a

middle size 500 MW Brown Coal Plant, the CO2

absorption column should be 24m x 26m.

For a large 5000MWcoal power station in China the

emission of CO2 is about 30 million ton per year. The

CCS cost is about 60-100$/per T CO2 and total need

about 2-3 billion US$.

Investments for separation equipment for CO2

capture will be huge indeed!

Pressure drop of Ф38 Pall Ring

Limitation of Pall Ring

0.4 0.6 0.8 11 2 4 6 8 1010

60

80100100

200

400

600

80010001000

2000

4000

ΔP

,

P

a/m

FV , m/s·(kg/m

3)

0.5

LW

m3/m

2·h

0

20

40

60

80

100

120

140

160

Super Mini Ring(SMR)

CFD Simulation

• Pall Ring SMR

CFD Simulation

CFD Simulation

PIV Measurements

PIV（particle image velocimetry）

Comparison of the Velocity vector of Pall ring and SMR packing

Plum Flower Mini Ring (PFMR) • Fei Weiyang, Wang Y D, Song X Y, Yin Y D, Sun L Y. Intensification of random packing via CFD simulation, PIV

measurement and traditional experiments. Journal of Chemical Technology and Biotechnology, 2003, 78(2-3): 142-145

•Fei, Weiyang; Sun, Lanyi; Guo, Qingfeng, Studies on a new random packing - Plum Flower Mini Ring, Chinese Journal of

Chemical Engineering, v 10, n 6, 2002, p 631-634

•H. Habaki, J. M. Perera, S. E. Kentish, G. W. Stevens and W Fei, CO2 Absorption Behavior with a Novel Random Packing:

Super Mini Ring, Separation Science and Technology, 42: 701–716, 2007

Comparison of pressure drop among PFMR, Pall Ring and Intalox(LW = 80 m3/m2·h)

1 10

100

1000

ΔP

, P

a/m

FV , m/s·(kg/m

3)

0.5

Ф 38 PFMR

Ф 38 Pall Rings

Ф 50 PFMR

Ф 50 Pall Rings

Ф 38 Intalox Saddle

Comparison of flooding velocity among PFMR, Pall Ring & Intalox Saddle

0 20 40 60 80 100 120 140 160 1800.5

1.0

1.5

2.0

2.5

3.0

3.5

UG

F , m

/s

LW

, m3/m

2·h

Ф 38 PFMR

Ф 38 Pall Rings

Ф 50 PFMR

Ф 50 Pall Rings

Ф 38 Intalox Saddle

10 20 40 60 80 100 2000.2

0.3

0.4

0.5

0.6

0.7

(HT

U) 2

5℃

,

m

LW

, m3/m

2·h

Ф 38 PFMR

Ф 38 Pall Rings

Ф 50 PFMR

Ф 38 Intalox Saddle

Comparison of mass transfer among PFMR, Pall Ring & Intalox Saddle

Comparison of mass transfer between PFMR & Mellapak (LW=80m3/(m2·h))

0.5 1.0 1.5 2.0 2.5 3.0 3.5

0.0

0.5

1.0

1.5

2.0

2.5

FG , (m/s)(kg/m

3)

0.5

(HO

L) 2

5o C

, m

50 PFMR

63 PFMR

Mellapak 125Y

Mellapak 250Y

49

Application of SMR &PFMR • Lube-oil refining;

• Aromatic separation;

• Phenol waste water treatment;

• LPG & gasoline de-sulfurization;

• CO2 Absorption & Solvent regeneration in

Ammonia plants;

• CO2 Absorption & Solvent regeneration for CTL;

• More than 80 SMR & PFMR columns have been put

into operation successful since 1990.

50

Application for CO2 absorption

• An existing Carbon Dioxide absorption

Column in Houlianhe Ammonia plant;

• Original design: i.d.2.2m, use 38mm Pall

Ring，3 packing bed(6.5m height each);

• Revamping using 38mm PFMR，Height of

Packing bed keep the same;

• Capacity increased 25％，Pressure drop

decrease 27％ and the solvent ratio

decrease 15％ after the revamping.

51

Apply for CO2 stripping : Case Study 1

• Existing solvent regeneration Column for CC in

Tianjin petrochemical plant:

• Original design: i.d.2.0m, use 50mm Intalox

Saddle，packing bed height is 18m;

• Revamping using 80mm PFMR，Height of

Packing bed keep the same;

• Capacity increased 105 while the liquid loading

increased 50% after the revamping.

52

Apply for CO2 stripping : Case Study 2

• Existing solvent regeneration Column for CC in

Dusangzhi petrochemical plant:

• Original design: i.d.1.3m, use 50mm Intalox

Saddle，packing bed height is 18.3m;

• Revamping using 80mm PFMR，Height of

Packing bed keep the same;

• Capacity increased 70％，while the liquid

loading increased 50%（ up to 140m3/m2hr）

after the revamping.

Case Study 2: Developing NRDC

Based on LDV and CFD

• Rotating Disc Contactor (RDC) is widely used in industry;

• RDC has good performance in lab, but often lost its efficiency in commercial application, especially for low interfacial tension systems and large diameter columns;

• It is essential to use advance LDV measur- ement & CFD simulation to improve our understanding and modify its structure;

RDC ( Rotating Disc Contactor ) is a

kind of widely used agitating

extraction column. It has:

High Capacity;

Easy to operate；

Widely used in refinery, fine

chemical industry such as lube oil

refining & etc；

Mass transfer efficiency of

commercial column with low inter-

phase tension decreases very quick；

Flow field of RDC in literature

True Flow field of RDC

CFD Simulation

Comparison

0

0.5

1

1.5

2

2.5

3

80 90 100 110 120 130 140 150

R

u( m

/ sec )

Experimental

Simulated

(a)

-0.04

-0.03

-0.02

-0.01

0

0.01

0.02

0 40 80 120 160

R( mm )

w( m

/sec )

Experimental

Simulated

(b )

-0.03

-0.02

-0.01

0

0.01

0.02

0.03

0 40 80 120 160

R( mm )

v( m

/sec )

Experimental

Simulated

( c )

RDC and NRDC

EXPERIMENTAL

HYDRODYNAMIC AND MASS TRANSFER EXPERIMENT

•

Fig.3 Mass transfer comparison between MRDC and

RDC( Vd=Vc=1.67x10-5m3/s)

0

2

4

0 40 80 120

N( rpm )

NT

U

RDC

MRDC

HYDRODYNAMIC AND MASS TRANSFER EXPERIMENT

•

Fig.4 Throughput capacity comparison between

MRDC and RDC (Vc=1.67x10-5m3/s)

0

0.04

0.08

0 40 80 120

N( rpm )

Vd(

m3 /s

)x10

3

RDC

MRDC

Application of MRDC • Revamping a existing 1.9m i.d. RDC with

MRDC;

• Since mass transfer efficiency increased about 20%, the solvent ratio decreased significantly;

• As a result, the capacity of the column increased 40% ;

• Many new larger MRDC extraction columns have been successful design and put into operation;

Papers • 费维扬，沈忠耀，汪家鼎, “液-液萃取转盘塔的特性及设计方法的探讨”(上、

下)，石油炼制, 1980, (10):10；(11):1

• Fei WY, Slater MJ, “New Look at the Hydrodynamic Behavior of Rotating Disc

Contactor”, J of Separation Process Technology, 1984, 5（1）：39

• 许宏庆，费维扬, “用LDV系统测量转盘萃取塔内流场”, 实验力学, 1995,

10(4):316

• 王运东，费维扬，戴猷元，汪家鼎. Numerical simulatoin and experimental

investigation of velocity fields in a rotating disc contactor. Tsinghua Science and

Technology, 1(4), 323~326, 1996

• 万银坤，王运东，费维扬. 用计算流体力学方法研究转盘塔内的流场，化学工

程，27（5），9-13，1999

• Fei, WY ， Y.D. Wang ， Y.K. Wan., Physical Modelling & Numerical Simulation of

Velocity Fields in Rotating Disc Contactor via CFD Simulation and LDV

Measurement. Chem. Eng. J., 78, 131-139, 2000

• Y.D. Wang, W.Y. Fei, J.H. Sun, Y.K. Wan. Hydrodynamics and mass transfer

performance of a modified rotating disc contactor (MRDC). Trans IChemE, Part A,

Chem Eng Res Des, 80(A4), 392-400, 2002

Case Study 3: Studies of Separation

Process Intensification for value adding

• Green processes for high value products are

very important for modern chemical

engineering, while separation science and

technology are essential.

• Two examples of isotope separation are

introduced simply as follows,

1. O18 separation;

2. B10 separation;

• Applications of oxygen-18 water

Applications of oxygen-18 water

Biology

Environment

Nuclear Medicine

Chemistry

Physics

Earth Chemistry

Physics：Target material

Chemistry：Research on chemical reactions

Biology：Photosynthesis,

Environment：Ascertain pollution source

Earth Chemistry：Hydrogeology

Nuclear Medicine：PET

PET（Positron Emission Tomography）

正电子断层扫描技术

Research on Optimized Design of Water Distillation

System for the Production of Oxygen-18 Isotope

O

AcO

OAc

OOAc

SO

O CF3

OAc

O

OAc

AcO

OAc

18F

OAc

O

OH

HO

OH

18F

OH水解

H218O

18F-

K2CO3/K222

K18F/K222

纯化

FDG产品72

Oxygen-18 water PET Imaging agent

synthesis flow chart

18

2H O

Nuclear reaction

From to FDG products for PET 18

2H O

Separation factor is extremely small 1.006

Vacuum distillation 13.3 kPa(100mmHg)

Low 18O natural abundance 0.2% to 98%

More than 2000 theoretical plates

High efficient packings

Multiple towers in cascade operation

Difficult to separation

High energy cost

Basic information

Optimized design is very important

Features of water distillation

Diagram of Square Cascade

Operating line in each column

Isotope Separation in Column trains

A

B

C

AC

AB

0 1

Relative Extraction Rate：

xt xb

Equilibrium Line

Operating Line

1 p p

L P P Py x x ( )x x

G G G G

P

G

G

P

L

P L

Cascade Theory for Isotope Separation

p

L G P,Lx Gy Px

Gao Yunhu1, Xu Zhihong2, Yu Zhaojun2, Fei Weiyang1, Study of concentration distributions of deuterium and oxygen-18 and influence of deuterium in heavy-oxygen water separation cascade., CIESC Journal, in press

2.2 水精馏体系的ASPEN模拟

ASPEN simulation of water distillation system for 18O production

D-7-G

D-7-L

D-6-G

D-6-L

D-5-G

D-5-L

D-4-G

D-4-L

D-3-G

D-3-L

D-2-G

D-2-L

D7D6D5D4D3 P

FEED

D

C7C6C5C4C3C2

P6P5P4P3P2P1

T7T6T5T4T3T2T1

W2-H W3-H W4-H W5-H W6-H

C-2 C-3 C-4 C-5 C-6 C-7

W1W2W3W4W6W5

D2

W1-H

Model to determine the total theoretical plates of each column

Surface treatment of 1200Y phosphor bronze wire gauze packing

High Performance Structured packing

Before After

0.5 1.0 1.5 2.0 2.5 3.0

0

500

1000

1500

2000

2500

Pressure drop per meter(Pa/m)

Fg [m/s*(kg/m3)

0.5]

1200Y

900Y

• 1200Y structured packing with inclined channel • 900Y structured packing with inclined channel

If Fg<2.14 ΔPm=714.9Fg-228.9 Pa/m

If Fg<1.77 ΔPm=573.7Fg-140.0 Pa/m

If 1.77≤Fg<2.78 ΔPm=876.4Fg-658.7 Pa/m

Hydrodynamics experiments results of 1200Y&900Y

structured packing with inclined channel

•Natural water

High Performance Structured packing

•Total reflux

0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4

8

10

12

14

16

18

20

22

24

26

Theoretical PLates per Meter

Fg [(m/s*(kg/m3)

0.5]

900Y Structured packing with inclined channel 1200Y Structured packing with inclined channel

0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2

14

16

18

20

22

24

26

Theoretical PLates per Meter

Fg [(m/s*(kg/m3)

0.5]

H2

16O/D2

16O

H2

16O/H2

18O

Nm = 2.108Fg2 – 10.95Fg + 30.30

Nm = 2.592Fg2 – 11.96Fg + 24.32

Experiments results of 1200Y&900Y

structured packing with inclined channel

in H216O/D2

16O distillation system

Experiments results of 1200Y structured

packing with inclined channel in H216O/D2

16O

and H216O/H2

18O distillation system

High Performance Structured packing

One of most complex separation system

• Production and Market Demand of Oxygen-18 Water

Company Country Annual production/kg

CIL USA 250

ISOTEC USA 120

MARSHALL Israel 100

ROTEM Israel 265

SONIC Russia 60

NIPPON SANSO Japan 100

Shanghai Research Institute of Chemical Industry

(上海化工研究院) China 50

Huayi Isotopes Company

(华益埃索托普) China 120

Annual production of main oxygen-18 water producer

Market demand increases by 20%~30% per year

Supply fails to meet the demand

50 dollars /gram

Jiangsu Huayi Technology Co., Ltd., is a private owned

enterprise covering an overall area of 200,000 square meters. It

integrate R&D, manufacture and marketing as a whole.

Products involve pharmaceuticals intermediates, pigments and

dyestuffs intermediates, stable isotopes and custom synthesis. At

the same time, we have two branches in Germany and Canada,

and keep a close relationship with Tsinghua University and many

famous enterprises abroad.

Separation Characteristics of Boron Isotopes in

Continuous Annular Chromatograph

• 10B is one of the most important materials having many usages especially for nuclear radiating protection.

• It is difficult to obtain high purity 10B from the nature mixture due to the concentration ratio of 10B to 11B is only about 0.24 while their structures are similar.

• The separation factor is lower than 1.05 and more than 100 equilibrium stages are needed.

A Continuous Annular Chromatograph (CAC) is set up with a 0.82m column

• The experimental system uses weakly basic resin (Diaion WA21J) as the absorbent; boric acid as the feed and water as the eluent.

• The effects of three factors (concentration of boric acid; rotating speed of CAC column and flow ratio of eluent to feed) on the separation performance of 10B are investigated.

• A 2-D-formulation of the mass balance equations of CAC is proposed.

• A numerical algorithm is developed to solve the coupled system of nonlinear convection diffusion equations in an iterative manner.

• The streamline diffusion method on an adaptively refined mesh is used to discrete the corresponding linear convection diffusion equations.

Typical experimental result

• In this column 10B and 11B can be separated effectively, and the relative isotopic abundance of 10B to 11B increased by 6%.

• The simulation of mathematical model for CAC coincides with experimental data well.

• The mass transfer coefficient and adsorption equilibrium constant for 10B in CAC column is little bigger than that of 11B.

• The preliminary results seem very good and collaborative researches are carrying on now.

References:

• Li Chengzhao; Wu Kejing; Qin Wei; Fei Weiyang. Simulation of separation in continuous annular chromatography, J Chem Ind Eng (China), 2013, 64(2):568-573.

• Thiele A, Falk T, Tobiska L, et al. Prediction of elution profiles in annular chromatography. Comp Chem Eng, 2001, 25(7): 1089-1101.

• Musashi M, Matsuo M, Oi T, et al. Chromatographic study on boron isotopic fractionation at high pressure. J Nucl Sci Technol, 2006, 43(4): 461-467.

Studies on Separation PI

for Low Carbon Development

• Introduction

• Separation Process Intensification

• Case Studies

•Summary

Summary

Chemistry and Chemical Industries are very important for

our life and our future.

However, they are facing challenges such as Globe Warming,

Energy & Resource Shortage, Pollution, Water Crisis and etc.

Separation science & technology are essential for green and

low carbon development of Chemical Industries. However,

there is a significant gap between fundamental research and

industrial applications. It is critical for us to bridging this gap.

It is important to organize international collaborative

researches projects to solve major problems such as CCS and

etc. We should work more closely to make sure that the

advanced, affordable and widespread technology will be ready

when we have to so.

CCUS & Sustainable Development

海洋储藏 地质储藏

农业利用

工业利用

EOR

电厂

水泥/钢铁/炼油企业

石化企业

未来

化工2利用

+CO2捕获

生物质 原煤

天然气

天然气+CO2捕获 原油

城市用气

Source：IPCC Special Report on Carbon

Dioxide Capture and Storage , 2005

Acknowledgements • Co-worker:

Prof. YD Wang; Prof. J Chen; Prof. GS Luo; Prof. W Qin; Prof. ZG Tan; Prof. G. Stevens; Prof. HZ Li;

• Graduate Students:

Dr. LY Sun; Dr. XY Song; Dr. NK Wan; Dr. YD Yin; Dr. JH Fan; Dr. N Ai; Dr. XL Zhao; Dr. DF Guo; Dr. X Gui; Ms. Y Liu; Ms. Y LI; Mr. YF Gao; Mr. KJ WU;

• State Key Lab of Chemical Engineering;

• Funding from NSFC & MOST;

Many Thank！